Supporting online information Lewis acid enhancement by ... · S1 Supporting online information...
Transcript of Supporting online information Lewis acid enhancement by ... · S1 Supporting online information...
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Supporting online information
Lewis acid enhancement by juxtaposition with an onium ion:
The case of a mercury stibonium complex
Tzu-Pin Lin,a Ryan C. Nelson,
b Tianpin Wu,
bJeffrey T. Miller*
b and François P. Gabbaï*
a
a Department of Chemistry, Texas A&M University, College Station, TX 77843-3255.
b Chemical Sciences and Engineering Division, Argonne National Laboratory,
Argonne, IL 60439-4837.
RECEIVED DATE
*To whom correspondence should be addressed. E-mail: [email protected]
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This PDF file includes:
Titration experiments
Fig. S1 1H NMR titration spectra of [2]
+ vs TBABr.
Fig. S2 199
Hg titration spectra of [2]+ vs TBAI, TBABr, and TBACl.
Derivation of the equation used to determine the 1:2 stability constant.
Computational section
Fig. S3 NBO plots showing 5d(Hg)→*(Sb-CPh1) interactions for [2]+, 2-F, [2-Cl2]
-,
and 2-I.
DFT optimized structural coordinates
X-ray Absorption Spectroscopy
Table S1 X-ray Absorption Spectra Fits.
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Titration experiments
General considerations. NMR spectra were recorded on Varian Unity Inova 400
FT NMR (399.59 MHz for 1H, 375.96 MHz for
19F, 100.45 MHz for
13C, 71.20 MHz
for 199
Hg) spectrometers at ambient temperature. Chemical shifts (given in ppm) are
referenced to residual 1H and
13C solvent signals, BF3-Et2O, and external neat HgMe2.
Fig. S1: 1H Spectra obtained by titrating [2]
+ against TBABr in DMSO-d6. The
concentration in [2]+ remained constant during the titration (2.23 × 10
-2 M).
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Fig. S2: 199
Hg spectra obtained by titrating [2]+ against TBAI, TBABr, and TBACl in
DMSO-d6. The concentration in [2]+ remained constant during the titrations (2.20 ×
10-2
M (left), 2.23 × 10-2
M (middle), and 2.23 × 10-2
M (right)).
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Derivation of the equation used to determine the chloride binding constants: (R =
2+, S = Cl
-)
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Computational section
Fig. S3: NBO plots showing the 5d(Hg)→*(Sb-CPh1) interactions for [2]+, 2-F,
[2-Cl2]-, and 2-I.
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DFT optimized structural coordinates
Complex [2]+
Method 1
Hg -0.227550 -2.039756 -0.137530
Sb 0.116902 1.043079 -0.080034
C -4.601759 -2.536969 -0.429023
H -5.299097 -3.369892 -0.290284
C 0.430868 3.931792 -1.282871
H 0.359810 3.443372 -2.262396
C -4.149616 -0.224987 -1.090259
C 3.931278 -3.488483 -0.412790
H 4.427621 -4.454549 -0.272586
C -3.793228 2.094331 -1.775976
H -4.166832 3.041993 -2.176520
C -2.432265 1.989634 -1.389667
H -1.806990 2.881986 -1.472930
C -2.299814 -1.675558 -0.296006
C -1.919564 0.795855 -0.881582
C 1.241835 0.204044 2.679389
H 2.199498 0.164893 2.148397
C -2.743818 -0.382802 -0.743284
C 4.000382 -1.134904 -1.078410
C 1.875605 -2.140713 -0.282933
C 0.049400 0.530339 2.000994
C 2.594603 -0.978469 -0.731101
C 0.456451 3.834184 1.160723
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H 0.404534 3.265013 2.095316
C 0.360121 3.184717 -0.085390
C -5.046550 -1.320049 -0.913512
H -6.100977 -1.174122 -1.174785
C 2.049887 0.351998 -0.874572
C -4.634436 1.010280 -1.609092
H -5.695927 1.084557 -1.872393
C 4.633702 -2.400500 -0.899125
H 5.694227 -2.491472 -1.160649
C 0.691411 5.973508 0.018439
H 0.820609 7.060026 0.059466
C 2.811349 1.402190 -1.387758
H 2.395948 2.409356 -1.475543
C -3.222903 -2.710740 -0.138461
H -2.887362 -3.696279 0.205804
C 4.744109 -0.038420 -1.602691
H 5.795494 -0.200591 -1.867145
C 0.596347 5.325513 -1.224487
H 0.651070 5.902689 -2.153593
C 2.547694 -3.353800 -0.123597
H 2.002689 -4.241230 0.219703
C -1.184903 0.560545 2.682308
H -2.114514 0.800347 2.153910
C -1.218812 0.265882 4.055406
H -2.174599 0.288044 4.589598
C 1.192472 -0.088829 4.052556
H 2.115339 -0.343493 4.584402
C 4.161638 1.203473 -1.774330
H 4.733941 2.043787 -2.179768
C 0.622007 5.229607 1.206316
H 0.696830 5.732394 2.176340
C -0.033929 -0.058320 4.737790
H -0.066652 -0.289493 5.807721
Method 2
Hg 0.133678 -2.059312 -0.207841
Sb -0.066562 1.028608 -0.004888
C -4.023420 -3.363333 -0.573567
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H -4.541686 -4.319282 -0.506049
C -0.237722 3.834899 -1.394200
H -0.200840 3.275874 -2.329900
C -4.035643 -0.975611 -1.054267
C 4.431920 -2.816354 -0.475146
H 5.068132 -3.696683 -0.390252
C -4.139884 1.400751 -1.563282
H -4.690373 2.283241 -1.886478
C -2.780476 1.528969 -1.199728
H -2.338357 2.522010 -1.226605
C -1.950309 -2.087478 -0.355738
C -2.046942 0.429719 -0.782836
C 1.167580 0.563351 2.781317
H 2.113332 0.706761 2.257053
C -2.629148 -0.883818 -0.718457
C 4.144685 -0.449663 -0.973828
C 2.206698 -1.819391 -0.308808
C -0.055181 0.607452 2.096586
C 2.731840 -0.539442 -0.665717
C -0.250760 3.912739 1.040275
H -0.223009 3.411157 2.008489
C -0.200838 3.179077 -0.151564
C -4.697139 -2.229654 -0.965749
H -5.756873 -2.273566 -1.220167
C 1.986057 0.687183 -0.750276
C -4.752921 0.173894 -1.477480
H -5.807951 0.064625 -1.733122
C 4.961117 -1.606858 -0.862516
H 6.022555 -1.514365 -1.095733
C -0.374235 5.965519 -0.245292
H -0.442683 7.053374 -0.281140
C 2.578242 1.870091 -1.162635
H 2.011426 2.797084 -1.205429
C -2.642699 -3.286632 -0.282333
H -2.121247 -4.204417 -0.006998
C 4.714874 0.780943 -1.392764
H 5.780013 0.808262 -1.627420
C -0.323487 5.229332 -1.434561
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H -0.351087 5.739402 -2.397526
C 3.047016 -2.918179 -0.212715
H 2.643225 -3.894700 0.058095
C -1.271464 0.405904 2.764343
H -2.220532 0.427024 2.227039
C -1.257078 0.165143 4.141457
H -2.197790 0.004821 4.668432
C 1.165406 0.321711 4.158290
H 2.111616 0.283301 4.698284
C 3.949481 1.917221 -1.500588
H 4.386905 2.861718 -1.821297
C -0.337587 5.308874 0.987263
H -0.376711 5.879335 1.915574
C -0.042838 0.123043 4.835182
H -0.037773 -0.070986 5.908333
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Complex 2-F
Method 1
Hg 0.002060 -2.041331 -0.129415
Sb 0.002978 1.110999 -0.397457
F 0.015116 1.855679 -2.325271
C -2.110002 -1.950890 -0.195829
C -2.053668 0.493347 -0.942844
C 4.196783 -0.753863 -0.819133
C -0.016666 0.358711 1.709720
C -2.744532 -0.735127 -0.638203
C 2.754079 -0.736032 -0.621825
C -4.135927 1.522349 -1.731640
H -4.641986 2.389153 -2.170874
C 0.002423 3.194073 0.219738
C 2.114201 -1.955333 -0.196807
C 1.189961 0.180215 2.421224
H 2.152847 0.291152 1.909344
C 4.159526 1.533138 -1.672579
H 4.670823 2.404994 -2.095400
C 2.068572 0.498444 -0.914090
C -4.848569 0.390980 -1.378940
H -5.935457 0.345619 -1.521428
C -2.888358 -3.074095 0.086118
H -2.408861 -4.003088 0.419272
C 0.003019 3.552470 1.580675
H 0.003311 2.784440 2.360469
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C -4.302262 -3.064941 -0.057919
H -4.882690 -3.964030 0.179643
C 1.176719 -0.152441 3.787435
H 2.123594 -0.291916 4.322329
C -4.186032 -0.751276 -0.843235
C 0.002643 4.198859 -0.770153
H 0.003843 3.894951 -1.820990
C -2.735217 1.569728 -1.509483
H -2.178682 2.461753 -1.806816
C -4.931480 -1.926615 -0.529100
H -6.017370 -1.910190 -0.684484
C 4.866257 0.393960 -1.333751
H 5.953744 0.346913 -1.470960
C 2.887791 -3.084948 0.072472
H 2.403984 -4.016601 0.391680
C 2.757477 1.581099 -1.459452
H 2.207191 2.479987 -1.747630
C 4.937022 -1.935937 -0.518290
H 6.023745 -1.920328 -0.667689
C -1.237413 0.215498 2.404842
H -2.189620 0.353857 1.879774
C 0.002652 5.552378 -0.395271
H 0.002622 6.329670 -1.168339
C 0.003337 4.909531 1.948189
H 0.003805 5.182933 3.009730
C 4.302169 -3.078956 -0.066549
H 4.878648 -3.983252 0.160630
C 0.002827 5.909550 0.962990
H 0.002853 6.966373 1.254068
C -1.252691 -0.116752 3.770847
H -2.210409 -0.228253 4.292799
C -0.045069 -0.304617 4.463741
H -0.056095 -0.564766 5.528461
Method 2
Hg 1.183400 -0.191889 -3.659187
Sb 3.304930 1.841171 -2.743737
F 1.822159 2.013554 -1.321460
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C 2.115364 -1.642186 -2.468643
C 3.830039 0.008267 -1.572583
C 0.037658 3.682638 -5.453287
C 4.624773 1.344538 -4.458105
C 3.222286 -1.289773 -1.633064
C 0.762181 2.666583 -4.717115
C 5.401657 -0.765361 0.129169
H 6.231185 -0.534124 0.797872
C 4.506627 3.347399 -1.764287
C 0.283223 1.319751 -4.795235
C 4.514907 2.053021 -5.663369
H 3.762590 2.835374 -5.776002
C 1.539167 5.410763 -4.640478
H 1.855697 6.452830 -4.587013
C 1.902061 3.093999 -3.959226
C 4.857526 -2.025380 0.090667
H 5.247393 -2.821257 0.728291
C 1.610358 -2.934271 -2.453086
H 0.763688 -3.200859 -3.089252
C 5.751321 3.724995 -2.282455
H 6.136020 3.263673 -3.193603
C 2.157400 -3.935859 -1.618235
H 1.735616 -4.941369 -1.625066
C 5.363622 1.756836 -6.736429
H 5.266769 2.312111 -7.670611
C 3.771206 -2.319419 -0.774969
C 4.013209 3.941972 -0.595129
H 3.040875 3.634646 -0.208699
C 4.881791 0.251004 -0.708115
H 5.336946 1.237716 -0.650646
C 3.215182 -3.626790 -0.794667
H 3.645766 -4.382779 -0.135571
C 0.450507 5.041273 -5.393381
H -0.118164 5.785517 -5.954554
C -0.825232 1.014383 -5.571177
H -1.190149 -0.013275 -5.627470
C 2.264247 4.427660 -3.923957
H 3.124620 4.752542 -3.340769
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C -1.093673 3.316088 -6.231984
H -1.622434 4.100252 -6.777035
C 5.583476 0.327252 -4.343450
H 5.670919 -0.246263 -3.419462
C 4.773993 4.918038 0.056595
H 4.392067 5.381354 0.967500
C 6.506779 4.702617 -1.624173
H 7.477379 4.996178 -2.026627
C -1.519352 2.008777 -6.297241
H -2.389524 1.738291 -6.895835
C 6.018610 5.298804 -0.456724
H 6.609115 6.061545 0.053714
C 6.432252 0.032740 -5.416991
H 7.173002 -0.762346 -5.316886
C 6.323104 0.746869 -6.614201
H 6.978617 0.510854 -7.454329
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Complex [2-Cl2]-
Method 1
Hg -1.954028 0.071533 -0.221871
Sb 1.089892 -0.056423 -0.219456
Cl -4.660895 0.190922 -0.278491
Cl 0.917517 -0.169540 -2.996917
C 0.879203 2.130266 -0.544437
C -1.829405 -2.089690 -0.168254
C -0.357571 2.832334 -0.373691
C -1.635209 2.210138 -0.153713
C 2.070895 2.790918 -0.816460
H 2.997574 2.228765 -0.964119
C 4.016680 -0.093881 0.931916
H 3.493711 -0.002804 1.890442
C 3.284091 -0.148308 -0.271229
C 0.896007 0.049056 1.979690
C 1.039882 1.280703 2.653159
H 1.242364 2.195681 2.084182
C 0.706069 -2.239475 -0.367841
C 0.542779 -5.049819 -0.414747
H 0.460820 -6.144694 -0.427611
C 0.915460 1.354937 4.051509
H 1.028704 2.321836 4.557359
C -0.598356 -2.825655 -0.276282
C 0.488084 -1.033313 4.137553
H 0.263450 -1.941458 4.710421
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C -0.652459 -4.284674 -0.283753
C 0.951872 4.938014 -0.710862
H 0.964332 6.034783 -0.762252
C -3.029609 -2.791427 -0.040627
H -3.965669 -2.225825 0.032564
C 1.853616 -3.013853 -0.490387
H 2.836787 -2.542656 -0.575733
C 0.617219 -1.105990 2.739253
H 0.485876 -2.071991 2.238406
C 1.774777 -4.432121 -0.522075
H 2.693273 -5.021940 -0.626863
C -3.076491 -4.211705 -0.028415
H -4.043642 -4.720544 0.072393
C -2.753543 3.017760 0.061424
H -3.728590 2.541090 0.214547
C 2.108706 4.208303 -0.914036
H 3.058206 4.709182 -1.137910
C 5.421665 -0.154003 0.913674
H 5.979279 -0.111578 1.857426
C 3.978031 -0.261607 -1.494237
H 3.405935 -0.302220 -2.429713
C 0.638032 0.197434 4.797087
H 0.533908 0.255489 5.887413
C -1.909808 -4.943259 -0.157069
H -1.926067 -6.041361 -0.165717
C -1.464364 5.058999 -0.209314
H -1.387653 6.153681 -0.252922
C -0.286069 4.288819 -0.431328
C -2.672730 4.436744 0.048570
H -3.578031 5.032031 0.223182
C 6.107504 -0.267264 -0.306088
H 7.203381 -0.313669 -0.319798
C 5.382774 -0.320342 -1.508319
H 5.910899 -0.408644 -2.465817
Method 2
Hg 1.333899 0.043206 1.448324
Sb -0.683752 0.294600 -0.813833
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Cl 3.114192 -0.337901 3.485387
Cl -0.059137 2.875277 -0.731111
C 1.154969 0.082778 -2.043082
C -0.325711 0.476743 2.734456
C 2.447834 -0.194878 -1.507869
C 2.760833 -0.299767 -0.114110
C 0.932422 0.187685 -3.402461
H -0.063971 0.406744 -3.785537
C -2.842239 -0.440806 -2.985639
H -2.700941 -1.446617 -2.587171
C -2.116729 0.636424 -2.456180
C -1.031448 -1.905478 -0.688650
C -0.354499 -2.785924 -1.547466
H 0.368006 -2.400190 -2.269020
C -2.039818 0.765999 0.884429
C -4.006609 1.353803 2.791711
H -4.761598 1.584398 3.547402
C -0.590259 -4.164372 -1.488055
H -0.051641 -4.834331 -2.161442
C -1.644556 0.763808 2.254916
C -2.171211 -3.814568 0.307039
H -2.873320 -4.209731 1.044002
C -2.682989 1.072702 3.223277
C 3.253363 -0.272188 -3.866167
H 4.082090 -0.413734 -4.564359
C -0.077983 0.506856 4.099796
H 0.932183 0.286381 4.451337
C -3.336345 1.043391 0.496673
H -3.612697 1.040025 -0.557375
C -1.936469 -2.435841 0.243328
H -2.463911 -1.773350 0.931859
C -4.333922 1.339083 1.455856
H -5.350770 1.555148 1.124778
C -1.090905 0.815520 5.037582
H -0.850969 0.833706 6.102777
C 4.063229 -0.587721 0.269881
H 4.288974 -0.659263 1.335904
C 1.988919 0.010800 -4.327562
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H 1.788284 0.099373 -5.396325
C -3.753965 -0.237184 -4.028421
H -4.311814 -1.085183 -4.430718
C -2.316546 1.921602 -2.980748
H -1.751669 2.757635 -2.563575
C -1.500636 -4.682058 -0.560927
H -1.678044 -5.758458 -0.507176
C -2.368744 1.092174 4.607426
H -3.163112 1.332640 5.318466
C 4.829829 -0.672893 -2.021882
H 5.619428 -0.807303 -2.765584
C 3.516363 -0.382147 -2.474666
C 5.097532 -0.777115 -0.675851
H 6.109407 -0.998597 -0.329974
C -3.948821 1.045190 -4.550915
H -4.659700 1.203497 -5.364968
C -3.228392 2.122684 -4.023679
H -3.375426 3.127689 -4.424785
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Complex 2-I
Method 1
Hg -1.438940 -0.011581 -0.402754
Sb 1.584636 0.029977 -0.033910
I -4.180415 -0.041887 0.648415
C 3.732460 0.033862 0.380725
C -1.070474 -2.130759 -0.713119
C -1.142812 2.115833 -0.736210
C 0.189657 4.116490 -1.400038
C 0.218044 -2.658910 -1.066511
C 4.155142 -0.042378 1.722251
H 3.418256 -0.097988 2.530994
C 0.840083 -0.051948 1.984571
C 6.487322 0.021148 1.020074
H 7.554324 0.016153 1.268573
C -0.039393 1.078370 3.947236
H -0.360294 1.999310 4.445991
C 0.749235 -1.292361 2.647236
H 1.033000 -2.221956 2.140603
C 4.708852 0.105243 -0.639969
H 4.412822 0.171363 -1.694544
C 0.137845 2.718746 -0.982320
C 1.409143 2.066461 -0.828397
C 1.461374 -1.943952 -0.979898
C 2.615791 2.716107 -1.077114
H 3.569804 2.207102 -0.923772
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C 1.439386 4.746856 -1.664850
H 1.433777 5.795107 -1.988363
C -2.291820 2.896919 -0.876662
H -3.270079 2.446303 -0.671485
C -0.863280 -4.844237 -1.580655
H -0.771453 -5.880067 -1.929808
C 6.077308 0.098394 -0.320933
H 6.821435 0.154438 -1.123428
C 0.310901 -4.037983 -1.533864
C 1.564234 -4.579825 -1.940119
H 1.589139 -5.614263 -2.304639
C 0.440881 1.135905 2.628317
H 0.480522 2.097574 2.104440
C 2.633475 4.067050 -1.510341
H 3.592424 4.559116 -1.705370
C 2.674740 -2.507832 -1.365687
H 3.610351 -1.953637 -1.263446
C 2.726288 -3.833042 -1.870311
H 3.688205 -4.256677 -2.178528
C -1.020859 4.855323 -1.538014
H -0.958702 5.904559 -1.851831
C -2.240543 4.260335 -1.272618
H -3.171240 4.831496 -1.369227
C -2.180902 -2.974893 -0.767070
H -3.163507 -2.580880 -0.481170
C -0.125591 -0.154263 4.614436
H -0.511799 -0.195244 5.638660
C 5.525410 -0.048627 2.038783
H 5.837897 -0.107758 3.087474
C 0.267020 -1.336732 3.965735
H 0.187849 -2.300665 4.480283
C -2.084974 -4.328983 -1.187444
H -2.985602 -4.953597 -1.210983
Method 2
Hg -1.444816 -0.044034 -0.368586
Sb 1.543588 0.031824 0.107986
I -4.388080 -0.216298 -0.116702
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C 3.727146 0.131395 -0.035901
C -1.087514 -2.044115 -1.075410
C -1.240500 2.064829 0.021557
C -0.037814 4.182350 -0.453386
C 0.196652 -2.670088 -1.020236
C 4.492280 0.424964 1.100516
H 4.011179 0.565450 2.069863
C 1.270298 0.037221 2.242934
C 6.519539 0.350682 -0.228841
H 7.604895 0.434907 -0.303028
C 1.051376 1.239653 4.327832
H 0.994831 2.183893 4.870579
C 1.165960 -1.183444 2.922484
H 1.195251 -2.129041 2.378837
C 4.369267 -0.055610 -1.271265
H 3.793282 -0.299587 -2.165440
C -0.029275 2.736848 -0.331406
C 1.226257 2.101598 -0.567267
C 1.402092 -2.066012 -0.551447
C 2.342048 2.789220 -1.006090
H 3.289097 2.278273 -1.167626
C 1.117777 4.864911 -0.917734
H 1.067655 5.949276 -1.033460
C -2.355323 2.819053 0.352131
H -3.284526 2.309185 0.609333
C -0.815287 -4.715469 -1.998749
H -0.701604 -5.748315 -2.332996
C 5.759588 0.057048 -1.366818
H 6.249355 -0.087916 -2.330672
C 0.315900 -4.051038 -1.457949
C 1.550462 -4.740574 -1.335109
H 1.596398 -5.781164 -1.661881
C 1.204298 1.252283 2.937682
H 1.259446 2.203858 2.407261
C 2.277867 4.187044 -1.215499
H 3.159090 4.715207 -1.578919
C 2.591665 -2.764691 -0.436852
H 3.490395 -2.279564 -0.061117
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C 2.664634 -4.125462 -0.813558
H 3.605737 -4.663611 -0.702468
C -1.213730 4.900419 -0.113379
H -1.204798 5.988409 -0.201722
C -2.340038 4.233040 0.312691
H -3.240007 4.786933 0.582863
C -2.158736 -2.746809 -1.607634
H -3.141636 -2.274985 -1.637622
C 0.956197 0.024267 5.014481
H 0.827974 0.019869 6.098063
C 5.885197 0.532056 1.003027
H 6.472474 0.756752 1.894574
C 1.010963 -1.184618 4.312857
H 0.923564 -2.133349 4.843810
C -2.026956 -4.070466 -2.086655
H -2.896550 -4.579895 -2.503363
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Table S1 X-ray Absorption Spectra Fits.
Sb and Hg XANES and EXAFS Fits
Sample XANES
Edge
Oxidation
State
Scatter N R, Å 2
(x
103)
Eo,
eV
Sb K-edge
30,492.0
Sb+3
Sb-C
3.1
2.14
0.0
-1.5
30,493.3
Sb+5
Sb-C
4.1
2.09
0.0
-2.0
30,493.3
Sb+5
Sb-C
4.2
2.11
0.0
-3.1
30,493.3
Sb+5
Sb-C
3.8
2.13
0.0
-1.5
30,493.2
Sb+5
Sb-C
4.1
2.08
0.0
-1.3
Hg L3 Edge
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12,284.6
Hg+2
Hg-C
2.0
2.09
0.0
-0.1
12,285.7
Hg+2
Hg-C
2.0
2.10
1.5
-0.5
12,285.5
Hg+2
Hg-C
1.9
2.06
1.5
-3.5
12,285.7
Hg+2
Hg-C
1.9
2.06
1.5
-2.8
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